Unsubstituted and polymeric lactone colorants for coloring consumer products

ABSTRACT

This invention relates to unsubstituted and polymeric leuco colorants for use as consumer product additives to indicate a product function by color change, to make attractive or distinctive visual effects, or to provide latent or delayed color generation. The colorants may be present in a stable, colorless state and may be transformed to an intense colored state upon exposure to certain physical or chemical changes. Alternatively, the colorants may be transformed from one color to another color upon exposure to certain physical or chemical changes. The colored form of the unsubstituted or polymeric leuco colorant may be transient, since the colorant can revert back to its colorless form or its original color after the physical or chemical activation has been removed or changed. Polymeric leuco colorants are typically comprised of at least two components: at least one leuco chromophore component and at least one polymeric component.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to US Provisional Patent ApplicationNo. 60/900,589, entitled “Unsubstituted and Polymeric Leuco ColorantsFor Coloring Consumer Products” which was filed on Feb. 9, 2007, and isentirely incorporated by reference herein.

TECHNICAL FIELD

This invention relates to both unsubstituted and polymeric leucocolorants for use as consumer product additives to indicate a productfunction by color change, to make attractive or distinctive visualeffects, or to provide latent or delayed color generation. These typesof colorants may be present in a stable, substantially colorless stateand may be transformed to an intense colored state upon exposure tocertain physical or chemical changes such as, for example, exposure tooxygen, the addition of reducing agents, ion addition, exposure tolight, and the like. These types of colorants may also be present in astable, colored state and may be transformed to a different coloredstate upon exposure to certain physical or chemical changes. The coloredform of the unsubstituted or polymeric leuco colorant may be transient,since the colorant can revert back to its colorless form or originalcolor after the physical or chemical activation has been removed orchanged. Some applications would benefit from leuco colorants thatgenerate color and then remain substantially colored. Polymeric leucocolorants are typically comprised of at least two components: at leastone leuco chromophore component and at least one polymeric component.These environmentally induced, reversibly-adaptable colorants may beideal for use in laundry care compositions, household cleaners, inkcompositions, waxes, paints, paper, films, foams, thermoplasticmaterials, coatings and any other product wherein the addition of acolorless polymeric leuco colorant that exhibits color effects only uponexposure to certain environmental catalysts is desired. It is also clearthat products can be colored with stable conventional colorants inaddition to the leuco colorant, such that a change in shade is observedupon color generation from the leuco colorant.

BACKGROUND

Leuco dyes are known in the prior art to exhibit a change from acolorless or slightly colored state to a state of dark color uponexposure to controlled chemical or physical changes. For example,triphenylmethane (“TPM”) compounds, one class of leuco dyes, are usefulin applications such as photoimaging and typewritten ribbons wherebymicroencapsulated TPMs are brought into contact with an acid source andimages are generated when pressure or heat is applied. These dyes aredescribed, for example, in Chemistry and Applications of Leuco Dyes(edited by Ramaiah Muthyala, pp. xi-xiii; 151-152).

The use of polymeric colorants for coloring consumer products is wellknown in the prior art. As one non-limiting example, the use ofwhitening agents, either optical brighteners or blueing agents, intextile applications is known. As textile substrates age, their colortends to fade or yellow due to exposure to light, air, soil, and naturaldegradation of the fibers that comprise the substrates. Thus, thepurpose of whitening agents is generally to visually brighten thesetextile substrates and counteract the fading and yellowing of thesubstrates.

Previous attempts to add bluing agents to fabric care products have usedpreformed pigments or dyes such as azo dyes, triaminotriphenyl methanecompounds, triphenyl methane compounds and anthraquinone colorants. U.S.Pat. No. 4,137,243 to Farmer teaches polymeric anthraquinone-derivedcolorants which exhibit improved light and alkali fastness properties.Farmer also discloses that these colorants may be incorporated intodetergent compositions to provide coloration or blueing effect for thedetergent composition. These types of colorants must therefore be alkalifast, in order to withstand the alkaline conditions of the detergentcomposition. The colorants should also be water fugitive so as to notstain the textile articles washed with the colored detergentcomposition. However, Farmer does not disclose polymeric leuco colorantsthat have the ability to transform from a colorless to a colored stateupon exposure to certain physical or chemical changes.

U.S. Pat. No. 5,039,782 to Langer et al. discloses a copolymer whiteningagent that contains a fluorescent group and a hydrophilic group. Thewhitening agent is preferably 4,4′-bis(carbomethoxystilbene), and thehydrophilic group is preferably a mixture of polyethylene glycol andethylene glycol. The copolymer optionally contains a hydrophobic monomerportion, such as polyethylene terephthalate, in order to better adherethe polymer to a hydrophobic surface (like polyester fabric or soiledcotton fabric). The resulting copolymer provides dual functionality as awhitening agent and for providing soil release to fabrics. However, itis apparent from the test data provided in Table 3 of the reference thatthe copolymer fails to provide adequate whitening for soiled cottonfabrics without the addition of a second whitening agent (i.e.,Tinopal). Furthermore, Langer et al. fail to disclose polymeric leucocolorants that exhibit a reversible transformation from a colorless to acolored state.

US Patent Application Publication No. 2005/0288206 to Sadlowski et al.discloses the use of hueing dyes in laundry detergent compositions forcombating the yellowing of fabrics. The hueing dye is designed to avoidsignificant build up of the dye on fabric so that the fabric does notexhibit a bluish tint, for example, after repeated exposure to thehueing dye present in laundry detergent. The laundry detergentcomposition is comprised of a surfactant and a hueing dye. Thesurfactant may be anionic, nonionic, cationic, zwitterionic, and/oramphoteric in nature. The hueing dye is characterized by having a hueingefficiency of at least 10 and a wash removal value in the range ofbetween 30% and 80%. Exemplary dyes which exhibit these propertiesinclude certain categories of dyes that contain blue or violetchromophores, such as triarylmethane dyes, basic dyes, anthraquinonedyes, and azo dyes. However, this reference fails to disclose the use ofunsubstituted or polymeric leuco colorants as described by the presentinvention.

Thus, it is contemplated to be within the scope of the present inventionthat the polymeric leuco colorants described herein may be ideallysuited for use as whitening agents. Many of the whitening agents thatare commercially available exhibit a dark color, e.g. a dark blue color,when added to a laundry care composition, such as a laundry detergent,rinse aid, fabric softener, and the like. For instance, the triphenylmethane and thiazolium structures are positively charged coloredspecies. With colored species such as these, the amount of color isvisually apparent and may be an undesired shade for consumers. Powdereddetergent systems typically use colored speckles to reduce apparentcolor of the detergent by incorporation of color within the interior ofa speckle or granule. Liquid products often incorporate opacitymodifiers to reduce the apparent darkness of the product.

The need exists for an effective whitening agent that consumers can usewithout concern that the garments and other textile substrates will beirreversible stained with the laundry detergent composition thatcontains a whitening agent. Thus, the colorless polymeric leucocolorants described herein may be added to laundry care compositionswithout fear of staining, since these colorants are colorless when addedto the laundry machine and only exhibit color during the laundry cycleand/or upon exposure to ultraviolet light when the whitening effect isachieved.

The present invention offers advantages over U.S. Pat. Nos. 4,137,243and 5,039,782 and US Patent Application Publication No. 2005/0288206 asthis invention takes advantage of colorless compounds that can beconverted to colored compounds with the addition of certain physicaland/or chemical catalysts. Such compounds are useful for many consumerproducts, including, but not limited to, their use as whitening agentsin laundry care compositions. As whitening agents, the colored compoundsexhibit the desired wavelengths in the range of blue, red, violet,purple, or combinations thereof upon exposure to ultraviolet light (or,they absorb light to produce the same shades) in order to neutralize theyellowness of textile substrates and provide a brightening effect.

SUMMARY

This invention relates to unsubstituted and polymeric leuco colorantsand to the method of using such latent colorants in consumer products.Consumer products include, for example laundry care compositions andother household cleaning compositions, as well as any other householdtextile and non-textile chemical composition. This invention alsorelates to consumer products that comprise such unsubstituted andpolymeric leuco colorants.

DETAILED DESCRIPTION

All patents, published patent applications, and any other publicationsmentioned in this patent application are herein incorporated entirely byreference.

The present invention relates to several preferred class of leuco dyeswhich have been discovered to exhibit selective fugitivity, i.e.designed for selective staining or non-staining characteristics in theirpolymeric form and to also demonstrate the color change transformationwhen exposed to certain physical or chemical changes. Leuco dyes includethe following classes of compounds: spirobenzopyrans,spironaphthooxazines, spirothiopyrans, leuco quinones, leucoanthraquinones, thiazine leuco colorants, oxazine leuco colorants,phenanzine leuco colorants, phthalide based leucos, tetrazolium basedleucos, triphenylmethanes, triarylmethanes, fluorans, and leucodiarylmethanes. Potentially preferred classes of leuco compounds mayinclude phthalide triphenylmethane, triaminotriphenyl acetonitriles, andmethylene blue colorants. It is contemplated that the unsubstituted andpolymeric leuco colorants of the present invention may or may not beencapsulated for use depending on the desired end use of the productcontaining the colorants.

Triphenylmethane (“TPM”) structures of the N,N disubstituted diamino andtriaminophenyl methane compounds produce bluish shades that aredecolorized by complexation or reaction with strong ions. Examples ofsuitable ions include, for example, hydroxyl ions, cyanide ions, cyanateions, and mixtures thereof. The highly alkaline environment needed toproduce hydroxyl ions is typically not suitable for products in theneutral to acidic pH range. The cyano product is colorless until exposedto ultraviolet (“UV”) light. Upon exposure to UV light, the originalblue color is generated and the bluing effect is observed. A laundrycare composition may be colored to a consumer pleasing level, and theamount of bluing on the treated textile substrate may be adjusted to themost desirable level. It is also noted that at least some of thecolorants of the present invention possess the ability to provide alatent color that is stable to conditions that degrade the coloredspecies. For example, the triphenyl acetoniltrile leuco colorants arestable to strong base and heat while the colored versions degrade. Theleuco form of methylene blue is stable to strong reducing agents whilemost classes of colorants are irreversibly decolorized.

In another embodiment, one approach may be to use colorless bluecolorant precursors that are sensitive to oxygen. For example, methyleneblue can be reduced to its colorless leuco form. For a practicalapplication, a small amount of reducing agent can be added at thebottling stage to convert the colorant to its colorless form in theclosed bottle. Suitable reducing agents include hydrosulfite, reducingsugars, and the like, and mixtures thereof. Thiazolium or othermericyanine dyes may be converted to colorless forms by ion addition.

Finally, blends of conventional optical brighteners or bluing agents andcolorless bluing agent precursors can be used to provide whiteningeffects, whether the effect is achieved immediately upon application orwhether it is formulated to provide an increased bluing effect over timeor on color generating exposure.

Examples of suitable polymeric constituents that comprise the leucopolymeric colorants include polyoxyalkylene chains having multiplerepeating units. Preferably the polymeric constituents includepolyoxyalkylene chains having from 2 to about 20 repeating units, andmore preferably from 2 to about 10 or even from about 4 to about 6repeating units. Non-limiting examples of polyoxyalkylene chains includeethylene oxide, propylene oxide, glycidol oxide, butylene oxide andmixtures thereof.

The polymeric leuco colorant of the present invention may becharacterized by the following structure:

wherein:

-   R₁=H, dialkyl amine, diarylamine, alkylamine, hydroxyl, halogen,    O-alkyl, or polyalkylene oxide amine;-   R₂=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or    glycidylether-polyalkylene oxide wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   R₃=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or    glycidylether-polyalkylene oxide wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   R₄=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or    glycidylether-polyalkylene oxide wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   R₅=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or    glycidylether-polyalkylene oxide wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   wherein X=alkyl, H, sulfonate, or carboxylate; G₁₋₃, Y, and Z are    independently selected from the group of alkyl, H, halogen, nitro,    and O-alkyl;-   wherein L=C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite,    nitrile, alkyl amine, imidazole, arylamine, polyalkylene oxide,    alkylsulfide, aryl sulfide, or phosphine oxide;-   wherein X and G₁ taken together may form an aromatic or    heteroaromatic ring;-   wherein Y and G₃taken together may form an aromatic or    heteroaromatic ring;-   wherein Z and G₂ taken together may form an aromatic or    heteroaromatic ring;-   wherein R₂ and G₂ taken together may form an aromatic or    heteroaromatic ring;-   wherein R₄ and G₃ taken together may form an aromatic or    heteroaromatic ring.

The polymeric leuco colorant of the present invention may also becharacterized by the following structure:

wherein:

-   R₁=H, alkyl, aryl, or alkyl-aryl wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   R₂=H, alkyl, aryl, or alkyl-aryl wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure;-   R₃=H, polyalkylene oxide, or glycidylether-polyalkylene oxide    wherein the terminal group is selected from hydroxide, C₁-C₁₈ alkyl    ester, and an amino substituted with H, C₁-C₁₈ alkyl, alkyleneoxide    residue, or ammonium quaternary salts derived from alkylation of the    amino substituted structure;-   R₄=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or    glycidylether-polyalkylene oxide wherein the terminal group is    selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino    substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium    quaternary salts derived from alkylation of the amino substituted    structure; and-   R₅=H, alkyl, or halogen; and R₆=H, alkyl, or halogen.

In one aspect, suitable polymeric leuco colorants are set forth in Table1 below. The corresponding chemical names, as determined by ChemFindersoftware Level:Pro; Version 9.0 available from CambridgeSoft, Cambridge,Mass., U.S.A., for such colorants are respectively provided in Table 2below.

TABLE 1 Structures for Polymeric Leuco Colorants (includes fluorans andlactone-TPM) Col- orant Structure 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

TABLE 2 Chemical Names for Structures Provided in Table 1 Colorant IUPACName 1(4-Dimethylamino-phenyl)-bis-(4-{ethyl-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-2-methyl-phenyl)-acetonitrile 2Bis-{4-[benzyl-(2-{2-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethyl)-amino]-phenyl}-(4-dimethylamino-phenyl)-acetonitrile 3(4-Dimethylamino-phenyl)-bis-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-propyl}-[2-(2-hydroxy-ethoxy)-propyl]-amino}-2-methyl-phenyl)-acetonitrile 4(4-Dimethylamino-phenyl)-bis-[4-((2-hydroxy-3-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-propyl)-{2-hydroxy-3-[2-(2-hydroxy-ethoxy)-ethoxy]-propyl}-amino)-phenyl]-acetonitrile5(4-Dimethylamino-phenyl)-bis-[4-((2-hydroxy-3-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-propyl)-{2-hydroxy-3-[2-(2-hydroxy-ethoxy)-ethoxy]-propyl}-amino)-2-methyl-phenyl]-acetonitrile 6Bis-[4-(benzyl-{2-hydroxy-3-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-propyl}-amino)-2-methyl-phenyl]-(4-dimethylamino-phenyl)-acetonitrile7Bis-{4-[benzyl-(2-{2-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethyl)-amino]-2-methyl-phenyl}-(4-dimethylamino-phenyl)-acetonitrile 8(4-Dimethylamino-phenyl)-bis-[4-((2-hydroxy-3-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-propyl)-{2-hydroxy-3-[2-(2-hydroxy-ethoxy)-ethoxy]-propyl}-amino)-2-methyl-phenyl]-acetonitrile 9Bis-[4-(benzyl-{2-hydroxy-3-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-propyl}-amino)-phenyl]-(4-dimethylamino-phenyl)-acetonitrile 10(4-Dimethylamino-phenyl)-{4-[{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-(2-{[2-(2-hydroxy-ethoxy)-ethyl]-phenyl-amino}-ethyl)-amino]-phenyl}-{4-[[2-(2-hydroxy-ethoxy)-ethoxy-ethyl]-(2-{[2-(2-hydroxy-ethoxy)-ethyl]-phenyl-amino}-ethyl)-amino]-phenyl}-acetonitrile11(4-Dimethylamino-phenyl)-bis-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-acetonitrile 12Bis-(4-{bis-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-phenyl)-(4-dimethylamino-phenyl)-acetonitrile 132-[2-(2-{{4-[(4-Dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-methoxy-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 142-[2-(2-{{4-[Butoxy-(4-dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 152-[2-(2-{{4-[(4-Dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-phenoxy-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 162-[2-(2-{{4-[(4-Dimethylamino-phenyl)-dodecyloxy-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 17{1-[(4-Dimethylamino-phenyl)-bis-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-methyl]-1H-pyridin-4-ylidene}-dimethyl-ammonium; chloride 182-[2-(2-{{4-[(4-Dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-imidazol-1-yl-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 192-[2-(2-{{4-[(4-Dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-morpholin-4-yl-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 202-[2-(2-{{4-[(4-Dimethylamino-phenyl)-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-phenylamino-methyl]-phenyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethanol 216-Dimethylamino-3-(4-dimethylamino-phenyl)-3-(4-{{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethyl}-[2-(2-hydroxy-ethoxy)-ethyl]-amino}-phenyl)-3H-isobenzofuran-1-one223-{4-[Bis-(2-{2-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethyl)-amino]-phenyl}-6-dimethylamino-3-(4-dimethylamino-phenyl)-3H-isobenzofuran-1-one 232-{2-[2-(2-{2-[6-((4-Dimethylamino-phenyl)-{1-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-1,2,3,4-tetrahydro-quinolin-6-yl}-methoxy-methyl)-3,4-dihydro-2H-quinolin-1-yl]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethanol 242-{6-Diethylamino-2-[[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxymethyl)-amino]-9H-xanthen-9-yl}-fluoran25 Sodium;2-[bis-(4-{bis-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-phenyl)-methoxy-methyl]-benzenesulfonate 26Bis-(4-{bis-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-phenyl)-phenyl-acetonitrile 272-(2-{2-[2-(2-{{4-[(4-{Bis-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-phenyl)-methoxy-phenyl-methyl]-phenyl}-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethanol 28Sodium;2-[bis-(4-{bis-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-amino}-phenyl)-dodecyloxy-methyl]-benzenesulfonate

The Colorants provided in Tables 1 and 2 vary in the way they aretransformed from their colorless to colored state. For example,Colorants 1-12 can generate color upon exposure to UV light. Colorants13, 16, 17, 19 and 28 can generate color upon exposure to heat.Colorants 13-16, 18, 21 and 24 generate color upon solvation or ionaddition (halochromics). Colorants 21, 22, and 24 generate color onexposure to acid. The methylene blue leuco dye family generates color onexposure to air.

There are a wide variety of possible applications of polymeric leucocolorants. Possible uses of these colorants include, for example, spraypattern indicators that are applied in a colorless state and thendevelop color upon exposure to UV light or oxygen. Alternatively, theinverse situation may be conceivable wherein a spray pattern indicatoris applied to a substrate in a colored state and its color disappearsafter exposure to a chemical or physical catalyst, such as UV light oroxygen.

Other uses of the polymeric leuco colorants of the present inventioninclude their incorporation as additives for color change in consumerproducts such as, for example, products packaged in opaque containersthat, when initially dispensed, are colorless but develop color uponexposure to air or light or water. This application may be useful inshowing activation or evenness of application. Another embodiment mayinclude an initially conventionally colored liquid product that changescolor after being dispensed from a container. For instance, the productmay change from yellow to green by the addition of a blue shade of thecolorant. A variation of this concept may include the shade matchedcolor that becomes color balanced to a grey shade after the leuco colordevelops. This has the visual effect of turning from colored tocolorless, since grey shades are much more difficult to observe.

Another example of color change additives in consumer products includesproducts packaged in visually transparent containers that are made ofplastics or formulated plastics that block UV light. After dispensingfrom the container, a color may be formed by exposure to ambient UVlight. Yet another embodiment includes products that are packaged in UVtransparent containers where the shade of the product depends ondirection and intensity of light—the color intensity being greatest nearthe wall of the container and decreasing into the interior of thecontainer. The distance of color formation may be dependent upon lightintensity, rate of color migration, and formulation of other lightabsorbers contained therein.

Other uses of polymeric leuco colorants may include transparentcontainers (e.g. thermoplastic containers) with negative image printedwith UV absorbing but visually transparent image. The color change inthis embodiment may occur in the UV exposed surface liquid to provide animage or logo that is present in the liquid product. Other uses includeincorporation of polymeric leuco colorants into molded plastic partsand/or containers that also contain high levels of UV blocker so thatthat the plastic part or container can only change color under very highintensity light. This application may also provide containers that havelogos or other design features that are difficult to produce byconventional means. It may also allow for covered sections on sealedcontainers that reveal tampering when exposed to UV light.

Further examples of the use of the polymeric leuco colorants includeincorporation into consumer products such as toilet bowl products thatare protected from light in the water tank but then turn color uponexposure to UV light when dispensed into the toilet bowl; coloredemulsions that allow only surface penetration of light giving a twocolor effect; solid consumer products like soap bars, bath powders, andlaundry powders wherein the surface is colored but the interior containsthe original color; and tamper evident seals and messages printed withinks containing colorless polymeric leuco colorants that, when exposedto light or air, transform to their colored state.

It is also contemplated that the polymeric leuco colorants may beincorporated into children's creative art products such as, for example,finger paints that change color during use; colorless paper thatgenerates color when painted with water or pH adjusting fluids; shadowbox image formation prepared by placing objects on paper or film coatedwith polymeric leuco colorants and then exposing the substrate to UVlight; preventing additional color formation on a substrate by asuitable mechanism like covering the substrate with a UV absorbing filmor coating; crayons or soft pencils that write one color and thendevelop a second color upon exposure to UV light; colored liquid markersand pens that dispense one shade and then change color; and molding clayproducts that change surface color upon exposure to oxygen or UV light.

Other embodiments include incorporation of polymeric leuco colorantsinto cosmetic formulations and compositions for the purpose of providinga lightening or “glowing” effect upon exposure to oxygen or UV light.This includes coloration effects for hair wherein color change occursupon outdoor exposure or the removal of intense light. The colorants mayalso be used for tinting films for housing and automobile windows thathave the effect of lightening in a low light environment. The colorantsmay also be used as expiration date indicators, temperature indicators(e.g. meat cooking temperature indicators), and fuel indicators formeasuring the presence of water.

Other possible applications for the unsubstituted and polymeric leucocolorants described herein include: pattern indicator for cleaningcompositions (such as coverage indicators for mopping, cleaning, carpolishing, etc.); image development over time with UV exposure (such asa picture image that changes over time); light bulbs that change coloras they get hotter; wires that change color as they get hot or wet as asafety indicator; colorants combined with encapsulated triggers (such asa color that changes upon exposure to water etc. mixed with encapsulatedwater) that when pressure is applied provides color change (the colorantcan also be encapsulated); UV light and moisture triggers could be usedfor any number of lifetime timers; urine indicator for children's sheetsand/or mattresses (possibly a washable feature); and deodorant thatreleases bluing agent on exposure to sweat (valeric acid, etc.) toreverse the yellowing of white shirts in the arm pits.

The polymeric leuco colorants described in the present specification maybe incorporated for use as whitening agents into a laundry carecomposition. Laundry care compositions include, but are not limited to,laundry detergents and fabric care compositions such as, for example,liquid and/or powder laundry detergent formulations and rinse addedfabric softening (RAFS) compositions. Such compositions comprise one ormore of said whitening agents and a laundry care ingredient. Thewhitening agent may be present in the laundry care composition in anamount from about 0.0001% to about 10% by weight of the composition,more preferably from about 0.0001% to about 5% by weight of thecomposition, and even more preferably from about 0.0001% to about 1% byweight of the composition.

The laundry care compositions, including laundry detergents, may be insolid or liquid form, including a gel form. The laundry detergentcomposition comprises a surfactant in an amount sufficient to providedesired cleaning properties. The laundry detergent composition comprisesa surfactant in an amount sufficient to provide desired cleaningproperties. In one embodiment, the laundry detergent compositioncomprises, by weight, from about 5% to about 90% of the surfactant, andmore specifically from about 5% to about 70% of the surfactant, and evenmore specifically from about 5% to about 40%. The surfactant maycomprise anionic, nonionic, cationic, zwitterionic and/or amphotericsurfactants. In a more specific embodiment, the detergent compositioncomprises anionic surfactant, nonionic surfactant, or mixtures thereof.

The detergent compositions of the present invention may also include anynumber of additional optional ingredients. These include conventionallaundry detergent composition components such as non-tinting dyes,detersive builders, enzymes, enzyme stabilizers (such as propyleneglycol, boric acid and/or borax), suds suppressors, soil suspendingagents, soil release agents, other fabric care benefit agents, pHadjusting agents, chelating agents, smectite clays, solvents,hydrotropes and phase stabilizers, structuring agents, dye transferinhibiting agents, opacifying agents, optical brighteners, perfumes andcoloring agents. The various optional detergent composition ingredients,if present in the compositions herein, should be utilized atconcentrations conventionally employed to bring about their desiredcontribution to the composition or the laundering operation. Frequently,the total amount of such optional detergent composition ingredients canrange from about 0.01% to about 50%, more preferably from about 0.1% toabout 30%, by weight of the composition.

The whitening agent may be added to textile substrates using a varietyof application techniques. For application to textile substrates, thewhitening agent is preferably included as an additive in laundrydetergent. Thus, application to the textile substrate actually occurswhen a consumer adds laundry detergent to a washing machine. Similarly,rinse added fabric softener compositions are typically added in therinse cycle, which is after the detergent solution has been used andreplaced with the rinsing solution in typical laundering processes. Forapplication to paper substrates, the whitening agent may be added to thepaper pulp mixture prior to formation of the final paper product.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles or flakes. Various techniques for forming detergentcompositions in such solid forms are well known in the art and may beused herein. In one embodiment, for example when the composition is inthe form of a granular particle, the whitening agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The whitening agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, thewhitening agent, optionally including additional but not all componentsof the laundry detergent composition, may be provided in an encapsulatedform, and the whitening agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The colorant compositions of this invention, prepared as hereinbeforedescribed, can be used to form laundry care compositions and otherhousehold cleaning compositions, including without limitation, aqueouswashing solutions for use in the laundering of fabrics, solid surfacecleaners, dish and skin cleaners, and shampoos. As one example, aneffective amount of a laundry care composition containing the inventivecolorant may be added to water, preferably in a conventional fabriclaundering automatic washing machine, to form an aqueous launderingsolution. The aqueous washing solution so formed is then contacted,preferably under agitation, with the fabrics to be laundered therewith.

Additionally, it is noted that the leuco colorants may be modified asnecessary in order to provide stability of the colorant when added as aningredient to other chemical compositions. For example, certain groupsattached to the chromophore of the colorant composition may be modifiedto provide equilibrium and stability of the colorant in the desiredend-use application. For instance, the ionic strength of the end-useapplication, such as a chemical composition, may affect the equilibriumof the colorant. Accordingly, modifications to the colorant may be madeto polymer chains and other groups attached to the colorant, in order tostabilize the colorant and prevent the colorless version of the leucocolorant from changing to the colored version too quickly. As oneexample, modifications to the colorant may be needed in order tostabilize the colorless state of the colorant when added to certainsurfactant-containing compositions, such as laundry detergents and thelike. In surfactant-containing compositions, it may be desirable tomodify the colorant so that it has the same or very similar surfaceenergy and/or HLB properties as the surfactant-containing composition.

EXAMPLES

The following examples are provided to further illustrate theunsubstituted and polymeric leuco colorants of the present invention;however, they are not to be construed as limiting the invention asdefined in the claims appended hereto. In fact, it will be apparent tothose skilled in the art that various modifications and variations canbe made in this invention without departing from the scope or spirit ofthe invention. All parts and percents given in these examples are byweight unless otherwise indicated.

Sample Preparation General Procedure 1: For Nitrile Addition to TPM

The following general procedure was used, for example, to make Colorants1-12 and 26 from Tables 1 and 2.

A 4-necked 500 mL round bottom flask was equipped with a thermocouple,heating mantle, mechanical stirrer, an air inlet and an outlet connectedto an air scrubber bath containing a 10% solution of NaOH. The polymerictriphenylmethane (0.080 mol) was poured into the flask, followed by theaddition of sodium cyanide (2M solution, 0.080 mol). The air inlet wasturned on, making sure that the outlet was bubbling into the sodiumhydroxide bath solution. The mixture was heated to 70° C. for 3 hours,the temperature was then lowered to 25° C. and the alkaline solution wastaken to pH 6 using muriatic acid. Further purification may beaccomplished by adding activated carbon, heating the mixture to 50° C.and filtering off the activated carbon.

General Procedure 2: For Alkoxide TPM Addition

The following general procedure was used, for example, to make Colorants13-16, 23, 25, 27 and 28 from Tables 1 and 2.

To a solution of the TPM (0.01 mol) in the corresponding alcohol (6 mL)was added the sodium alkoxide (0.015 mol). The mixture was heated toreflux for 1 hour and then cooled. Removal of the excess alcohol wasdone via evaporation on a rotary-evaporator or via distillation.

Phenoxides were done in isopropyl alcohol and the excess phenols wereleft in the mixture.

General Procedure 3: For Amine TPM Addition

The following general procedure was used, for example, to make Colorants17-20 from Tables 1 and 2.

To a solution of the TPM (0.010 mol) in water (10 mL) was added 10%sodium hydroxide to a pH of 10. The mixture was heated at 70° C. for 2hours. The pH of the solution was then taken to 7 with muriatic acid.The mixture was then diluted with toluene followed by the addition ofthe corresponding amine (0.020 mol) and 5-6 drops of acetic acid. Themixture was heated to reflux and the water removed via dean starkdistillation. The toluene was evaporated from the mixture to obtain thedesired product.

General Procedure 4: For Lactone TPM

The following general procedure was used, for example, to make Colorant21 from Tables 1 and 2.

4-(4-Dialkylaminobenzoyl)-dialkylamino-3-benzoic acid (0.060 mol) andthe aniline alkoxylated (0.061 mol) were mixed together in aceticanhydride for 24 hours at room temperature. After the reaction wascompleted the pH was taken to 10 with 10% sodium hydroxide and theorganic phase was separated and used without further purification.Further purification can be accomplished by extraction of the desiredproduct into methylene chloride followed by removal of the solvent viaevaporation. Smaller sized alkoylates may be recrystalized from butanol.

General Procedure 5: For Fluoran Synthesis

The following general procedure was used, for example, to make Colorant24 from Tables 1 and 2.

2-(4-Dialkylamino-2-hydroxybenzoyl)-benzoic acid (0.01 mol) andp-anisidine alkoxylate (0.015 mol) were dissolved in 10 mL ofconcentrated sulfuric acid at 40° C. and thereafter stirred at roomtemperature for 48 hours. After completion of the reaction, the mixturewas poured into a mixture of 50 g ice and 50 mL of water. The mixturewas taken to pH 10 and the aqueous layer was removed.

Test Results Calculation of Whiteness: CIELab b* and Ganz and CIEWhiteness Index

Whiteness Index (“WI”) is a qualifying assessment of color that iscalculated by a formula which includes three components of colormeasurement—hue, saturation, and lightness—which is then indexed to astandard white value. Several whiteness formulas can be used to measurewhiteness on cellulose based substrates. Two common formulas are theGanz Whiteness Index and CIE Whiteness. Ganz Whiteness Index isexpressed by the formula: WI=(D*Y)+(P*x)+(Q*y)+C, where Y, x and y arecolorimetric values and D, P, Q and C are formula parameters. CIEWhiteness is expressed by the formula: WI=Y−(800*x)−(1700*y)+813.7,where Y, x and y are colorimetric values. Higher positive Ganz WI valuesindicate that more blueing, or whitening effect, is exhibited by thetreated cellulose based substrate. Further information is available inthe publication of Rolf Griesser, Ciba-Geigy Ltd, “Whiteness and Tint”,June 1993.

The surface color of an article may be quantified using a series ofmeasurements—L*, a*, and b*—generated by measuring the samples using aspectrophotometer. The equipment used for this test was a Gretag MacbethColor Eye 7000A spectrophotometer. The software program used was “Colorimatch.” “L” is a measure of the amount of white or black in a sample;higher “L” values indicate a lighter colored sample. A measure of theamount of red or green in a sample is determined by “a*” values. Ameasure of the amount of blue or yellow in a sample is determined by“b*” values; lower (more negative) b* values indicate more blue on asample.

Yet another measurement of the relative color of a substrate is DE CMC.DE CMC is a measure of the overall color difference for all uniformcolor spaces, where DE CMC represents the magnitude of differencebetween a color and a reference. The Gretag Macbeth Color Eye 7000ASpectrophotometer calculates DE CMC values based on wavelength andreflectance data for each sample.

Several polymeric leuco colorants from Tables 1 and 2 were tested forbluing efficiency. Test results are provided in Table 3. Lower (morenegative) CIELab b* values indicate that more bluing, or whiteningeffect, is exhibited by the treated cotton swatch.

Each sample was prepared by adding 0.5 grams of the colorant (0.1% basedon weight of the cotton swatch) to a solution containing 3 grams ofpowdered laundry detergent (AATCC powder laundry detergent) and 500 mLof room temperature water. Each colorant loading was corrected forabsorbance to assure equal amount of color units. The formulation wasthen added to a 100% cotton swatch and agitated for 10 minutes. Theswatch was removed from the liquid, the excess liquid was removed, andthe swatch was air dried. The cotton swatch was then measured for colorusing a Gretag Macbeth Color Eye 7000A spectrophotometer, as describedpreviously (“CIELab b* value before UV” and “DE CMC value before UV”).

The cotton swatch was then subjected to UV light exposure for 5 minutes.After exposure the cotton swatch was again read on the Gretag Macbethspectrophotometer (“CIELab b* value after UV” and “DE CMC value afterUV”).

TABLE 3 Rate of Bluing Efficiency in Detergent on 100% cotton textileCIELab b* CIELab b* DE CMC DE CMC Color Value Color Value Value beforeValue after Sample before UV after UV UV UV Colorant 9 0.59 −3.12 1.326.05 Colorant 11 1.03 −7.03 2.42 11.91 Colorant 12 1.22 −2.37 0.56 5.01

Thus, the polymeric leuco colorant of the present invention may beselected from the group consisting of Structure I and Structure II asshown below:

-   -   wherein:    -   R₁=H, dialkyl amine, diarylamine, alkylamine, hydroxyl, halogen,        O-alkyl, or polyalkylene oxide amine;    -   R₂=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₃=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₄=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₅=C₁-C₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   wherein X=alkyl, H, sulfonate, or carboxylate; G₁₋₃, Y, and Z        are independently selected from the group of alkyl, H, halogen,        nitro, and O-alkyl;    -   wherein L=C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite,        nitrile, alkyl amine, imidazole, arylamine, polyalkylene oxide,        alkylsulfide, aryl sulfide, or phosphine oxide;    -   wherein X and G₁ taken together may form an aromatic or        heteroaromatic ring;    -   wherein Y and G₃ taken together may form an aromatic or        heteroaromatic ring;    -   wherein Z and G₂ taken together may form an aromatic or        heteroaromatic ring;    -   wherein R₂ and G₂ taken together may form an aromatic or        heteroaromatic ring;    -   wherein R₄ and G₃ taken together may form an aromatic or        heteroaromatic ring.

Additionally, the polymeric leuco colorant of the present invention maybe selected from the group consisting of Structure I and Structure II asshown below:

-   -   wherein:    -   R₁=H, alkyl, aryl, or alkyl-aryl wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₂=H, alkyl, aryl, or alkyl-aryl wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₃=H, polyalkylene oxide, or glycidylether-polyalkylene oxide        wherein the terminal group is selected from hydroxide, C₁-C₁₈        alkyl ester, and an amino substituted with H, C₁-C₁₈ alkyl,        alkyleneoxide residue, or ammonium quaternary salts derived from        alkylation of the amino substituted structure;    -   R₄=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure; and    -   R₅=H, alkyl, or halogen; and R₆=H, alkyl, or halogen.

Also, the polymeric leuco colorant of the present invention may beselected from the group consisting of Structure I and Structure II asshown below:

-   -   wherein:    -   R₁=H, dialkyl amine, diarylamine, alkylamine, hydroxyl, halogen,        O-alkyl, polyalkylene oxide amine, or monoalkyl-polyalkyene        oxide amine;    -   R₂=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₃=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₄=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   R₅=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, or        glycidylether-polyalkylene oxide wherein the terminal group is        selected from hydroxide, C₁-C₁₈ alkyl ester, and an amino        substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, or        ammonium quaternary salts derived from alkylation of the amino        substituted structure;    -   wherein X_(n)=carbon or sulfur and n =1 when X=carbon and n=2        when X=sulfur;    -   G₁₋₃, Y, and Z are independently selected from the group of        alkyl, H, halogen, nitro, and O-alkyl;    -   wherein Y and G₃ taken together may form an aromatic or        heteroaromatic ring;    -   wherein Z and G₂ taken together may form an aromatic or        heteroaromatic ring;    -   wherein R₂ and G₂ taken together may form an aromatic or        heteroaromatic ring;    -   wherein R₄ and G₃ taken together may form an aromatic or        heteroaromatic ring.

The invention described herein encompasses a method for imparting colorto a composition comprises the steps of: (a) adding a sufficient amountof any of the Structure II polymeric colorants as described and shownherein to a composition; (b) exposing the composition of step “a” to aphysical or chemical change that causes Structure II to change to thecorresponding Structure I; and (c) optionally, eliminating the impartedcolor from the composition by removing the physical or chemical changefrom the composition and causing Structure I to change back to StructureII.

The invention described herein also encompasses a method for impartinghue to a surface comprising the steps of: (a) adding a sufficient amountof any of the Structure II polymeric colorants as described and shownherein to a cleaning composition; (b) exposing a surface to the cleaningcomposition of step “a;” and (c) imparting a physical or chemical changeto the composition of step “b” that causes Structure II to change to thecorresponding Structure I.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A polymeric leuco colorant selected from the group consisting ofStructure I and Structure II as shown below:

wherein: R₁=H, dialkyl amine, diarylamine, alkylamine, hydroxyl,halogen, O-alkyl, polyalkylene oxide amine, or monoalkyl-polyalkyeneoxide amine; R₂=C₁-C₁₈ alkyl, aryl, benzyl, polyalkylene oxide, orglycidylether-polyalkylene oxide wherein the terminal group is selectedfrom hydroxide, C₁-C₁₈ alkyl ester, and an amino substituted with H,C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium quaternary saltsderived from alkylation of the amino substituted structure; R₃=C₁-C₁₈alkyl, aryl, benzyl, polyalkylene oxide, or glycidylether-polyalkyleneoxide wherein the terminal group is selected from hydroxide, C₁-C₁₈alkyl ester, and an amino substituted with H, C₁-C₁₈ alkyl,alkyleneoxide residue, or ammonium quaternary salts derived fromalkylation of the amino substituted structure; R₄=C₁-C₁₈ alkyl, aryl,benzyl, polyalkylene oxide, or glycidylether-polyalkylene oxide whereinthe terminal group is selected from hydroxide, C₁-C₁₈ alkyl ester, andan amino substituted with H, C₁-C₁₈ alkyl, alkyleneoxide residue, orammonium quaternary salts derived from alkylation of the aminosubstituted structure; R₅=C₁-C₁₈ alkyl, aryl, benzyl, polyalkyleneoxide, or glycidylether-polyalkylene oxide wherein the terminal group isselected from hydroxide, C₁-C₁₈ alkyl ester, and an amino substitutedwith H, C₁-C₁₈ alkyl, alkyleneoxide residue, or ammonium quaternarysalts derived from alkylation of the amino substituted structure;wherein X_(n)=carbon or sulfur and n=1 when X=carbon and n=2 whenX=sulfur; G₁₋₃, Y, and Z are independently selected from the group ofalkyl, H, halogen, nitro, and O-alkyl; wherein Y and G₃ taken togethermay form an aromatic or heteroaromatic ring; wherein Z and G₂ takentogether may form an aromatic or heteroaromatic ring; wherein R₂ and G₂taken together may form an aromatic or heteroaromatic ring; wherein R₄and G₃ taken together may form an aromatic or heteroaromatic ring. 2.The polymeric colorant of claim 1, wherein R₁=dialkyl amine; X=carbon;G₁₋₃=H; Y=H; Z=H; R₂ and R₃ are alkyl, and wherein R₄ and R₅ arepolyalkylene oxide.
 3. The polymeric colorant of claim 2, wherein R₄ andR₅ independently contain between 2 and 20 repeating units ofpolyoxyalkylene oxide.
 4. The polymeric colorant of claim 3, whereinpolyoxyalkylene oxide is selected from the group consisting of ethyleneoxide, propylene oxide, glycidol oxide, butylenes oxide and mixturesthereof.
 5. A chemical composition comprising the polymeric colorant ofclaim
 1. 6. A detergent composition comprising the polymeric colorant ofclaim
 1. 7. A method for imparting color to a composition comprising thesteps of: (a) adding a sufficient amount of the Structure II polymericcolorant of claim 1 to a composition; (b) exposing the composition ofstep “a” to a physical or chemical change that causes Structure II tochange to Structure I; and (c) optionally, eliminating the impartedcolor from the composition by removing the physical or chemical changefrom the composition and causing Structure I to change back to StructureII.
 8. The method of claim 7, wherein the physical or chemical change ofstep “b” is selected from one of the following: the addition of acid,reaction with strong ions, the addition of solvent, and any mixturesthereof.
 9. A method for imparting hue to a textile substrate comprisingthe steps of: (a) adding a sufficient amount of the Structure IIpolymeric colorant of claim 1 to a laundry care composition; (b)exposing a textile substrate to the laundry care composition of step“a;” and (c) imparting a physical or chemical change to the compositionof step “b” that causes Structure II to change to Structure I.
 10. Amethod for imparting hue to a surface comprising the steps of: (a)adding a sufficient amount of the Structure II polymeric colorant ofclaim 1 to a cleaning composition; (b) exposing a surface to thecleaning composition of step “a;” and (c) imparting a physical orchemical change to the composition of step “b” that causes Structure IIto change to Structure I.